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電渣重熔易氧化元素控制的研究進展

Research progress on the control of reactive elements in remelted ingots during the electroslag remelting process

  • 摘要: 電渣重熔是重要的二次精煉技術,不僅可以去除鋼中雜質元素和非金屬夾雜物,還可以改善鑄錠的凝固組織進而提升鋼的力學性能. 若鋼中含有易氧化合金元素,如Al、Ti、Si、B和稀土元素,會與CaF2?CaO?Al2O3基重熔渣系中的不穩定組元發生化學反應,造成合金元素沿鑄錠高度方向分布不均勻現象. 為抑制電渣重熔過程易氧化元素的燒損,在電渣重熔溫度范圍內,分析CaF2?CaO?Al2O3基重熔渣系中各個組元對鋼中目標控制元素含量的影響,可以實現重熔渣系成分的準確設計,這取決于渣相和合金相中組元活度的準確計算. 除了在重熔渣系中添加對應元素的氧化物之外,CaF2?CaO?Al2O3基重熔渣系中公共組元CaO和Al2O3以及溫度對鋼中不同合金元素含量的影響也并不相同. 電渣重熔過程傳質模型預報結果的準確性依賴于對熔渣和鋼液中組元的熱力學活度、不同反應位置(電極端部、金屬熔滴、渣池和金屬熔池界面)溫度、傳質系數和幾何參數的準確估計,但不同電渣重熔操作、重熔渣系成分和鋼種對以上參數都有較大影響. 由于準確估計不同反應位置處的反應溫度和流體流動對傳質系數的影響比較困難,相比較熱力學分析,易氧化元素反應的動力學研究仍比較匱乏. 重熔渣系物性參數對鑄錠的表面和凝固質量同樣有重要影響,目前對含TiO2、SiO2、B2O3和稀土氧化物的重熔渣系的物性參數研究主要集中在黏度和結晶能力等方面,但對其活度的實驗室研究還未見報道. 低氟重熔渣系的開發越來越受到關注,針對低氟重熔渣系條件下鋼中易氧化元素控制的熱力學、動力學和熔渣物性參數研究還有待于進一步開展.

     

    Abstract: Electroslag remelting (ESR) is an important secondary refining technique that effectively removes impurities and nonmetallic inclusions, improves the solidification structure of ingots, and enhances the mechanical properties of steels. However, when steels contain easily oxidizable alloying elements such as Al, Ti, Si, B, and rare earth elements (REEs), strong chemical reactions can occur between these elements and unstable components in the CaF2–CaO–Al2O3-based ESR type slag system. These reactions take place in the slag–metal interface and result in uneven distribution of the alloying elements along the height of the remelted ingots, ultimately compromising the mechanical properties of the steels. To reduce the oxidation loss of these alloying elements during the ESR process, a precise design of the CaF2–CaO–Al2O3-based ESR slag composition is crucial. This design facilitates accurate control of the reactive alloying elements within their target composition range, which relies on the feasibility of calculating the thermodynamic activities of components in the slag and alloys employing ion–molecular coexistence theory and Wagner equation, respectively. In addition to incorporating the corresponding oxide additives into the ESR-type slag system to prevent oxidation loss of alloying elements in the electrode during the ESR process, the effects of common components such as CaO and Al2O3 in the ESR-type slag, as well as temperature, on the alloying element content can vary. For instance, controlling the Al and Ti contents in alloys is influenced by the combined effects of the CaO composition range and the remelting temperature, in addition to the presence of Al2O3 in the ESR-type slag. For B-bearing steels, the B content in alloys can be primarily controlled by the CaO content rather than by Al2O3. In the case of alloys containing REEs, such as La, Ce, and Y, the addition of CaO enhances the yield of these elements, while the addition of Al2O3 has a negative effect. The accuracy of mass transfer models during ESR not only relies on precise estimation of the thermodynamic activities of components in the slag and molten steel but also on factors such as temperatures at different reaction locations (e.g., electrode tip, metal droplet, interface between slag bath, and metal pool), mass transfer coefficients, and geometric parameters. However, the parameters above are substantially influenced by various factors, such as different ESR operation conditions, slag compositions, and steel grades. Due to the challenges in determining reaction temperatures and fluid flow within the ESR furnace, precisely estimating the mass transfer coefficients of the relative elements in the slag and metal phases at different reaction locations is difficult. Thus, kinetic studies of reactive elements are relatively scarce compared to thermodynamic analyses. Additionally, the physical parameters of the slag system play a crucial role in determining the surface quality and solidification characteristics of the ingots. Current research on the physical parameters of remelting slag systems containing TiO2, SiO2, B2O3, and rare earth oxides has primarily focused on viscosity and crystallization behavior. However, laboratory studies on the activities of these components remain limited. As the development of low-fluorine ESR-type slag systems attracts increasing attention, the need for relative fundamental research, specifically on the thermodynamics and physicochemical properties of low-fluorine slags, also rises. This research is essential for effectively controlling the contents of reactive alloying elements in the ESR remelted ingots.

     

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